CN108439533A - A method of the recycling synchronous with chromium of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water - Google Patents

A method of the recycling synchronous with chromium of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water Download PDF

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Publication number
CN108439533A
CN108439533A CN201810414761.XA CN201810414761A CN108439533A CN 108439533 A CN108439533 A CN 108439533A CN 201810414761 A CN201810414761 A CN 201810414761A CN 108439533 A CN108439533 A CN 108439533A
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chromium
waste water
ultraviolet light
composite drug
reduction composite
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CN108439533B (en
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黄先锋
王茜然
周化斌
郑向勇
张业健
金展
王奇
赵敏
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Cangnan Institute Of Cangnan
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Cangnan Institute Of Cangnan
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C02F2103/24Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physical Water Treatments (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a kind of methods of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium, belong to field of waste water treatment.A kind of reduction composite drug of the present invention/UV combinations processing copper complex with synchronize remove copper removal method, step is:A, it offers medicine:It is complexed in waste water to trivalent chromium and adds reduction composite drug and stir, wastewater pH is adjusted to 4~10;B, ultraviolet light:The waste water stirred evenly is handled by ultraviolet light, chromium is precipitated with precipitated form;C, waste liqouor:Chromium is recycled by the method for separation of solid and liquid.The safe efficient processing for process hides, plating, dyestuff etc. being complexed containing trivalent chromium waste water and the recycling of chromium can be achieved in the present invention.

Description

A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water is synchronous with chromium The method of recycling
Technical field
The invention belongs to field of industrial waste water treatment, specifically, being related at a kind of reduction composite drug joint ultraviolet light The method for managing the recycling synchronous with chromium of trivalent chromium complexing waste water.
Background technology
Trivalent chromium (Cr (III)) passivation gradually replaces toxic, harmful sexavalence chromium passivating and process hides work in electroplating technology The addition of chrome tanning agent leads to the generation of a large amount of trivalent chrome waste water in skill.Meanwhile having in plating and a large amount of uses of leather-making technology Machine complexing agent, such as EDTA, NTA, citric acid, tartaric acid and oxalic acid so that chromium is in waste water usually with stable complex pattern In the presence of.Complex state chromium has very high water solubility, and can be stabilized within the scope of extensive pH, heavy using absorption, chemistry The conventional methods such as shallow lake, coagulation are difficult to effectively remove.
The advanced oxidation processes such as ozone oxidation, photochemical oxidation and electrochemical oxidation are that waste water is complexed in current processing Cr (III) Common method, but using hydroxyl radical free radical (OH) strong oxidizing property destroy chelation structure while significant portion Cr (III) It is oxidized to Cr (VI), Cr (VI) high conversion rate is caused, increases subsequent processing difficulty.At present frequently with electric flocculation, Fe2+Reduction The methods of precipitation Cr (VI) that further removal contact break process is formed, and then a large amount of chromium-bearing sludge is produced, increase disposition Cost.In general, existing complexing wastewater treatment method is carried out by two steps, and generated by Cr (VI) formation, chromium-bearing sludge, The challenge of the factors such as processing cost.Therefore, being highly desirable exploitation, in-situ control Cr (VI) is generated simultaneously in contact break, and same The new technology of step recycling chromium, to reduce the generation of Cr (VI) and chromium mud.
High-level oxidation technology based on UV has been widely used in the degradation of useless Organic substance in water, by organic matter point The characteristic absorption relationship of chemical bond and light source in minor structure, organic matter can directly be degraded by absorbing photon, while can also By the active oxidation species generated in situ, such as hydroxyl radical free radical (OH), Superoxide radicalanion (O2·), single line oxygen (1O2) etc., carry out oxidative degradation.Studies have shown that Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound has good light sensitivity, irradiated in UV Under can by ligand metal electric charge transfer act on by light degradation.As under UV effects Cr (III) occurs for Cr (III)-citric acid also Former and citric acid decarboxylation procedure, restores the Cr (II) of generation in O2、O2·-It is transformed into under the action of the oxide species such as OH Cr (III) and Cr (VI), ligand change the small molecular organic acids such as acetic acid, formic acid, CO after decarboxylation2And H2O.Similarly, Cr (III) ligand metal electric charge transfer can also occur under uv illumination for-EDTA, along with the decarboxylation of Cr (III) reduction and EDTA Process, final product are Cr (III), Cr (VI), small molecular organic acid (glycine, glyoxalic acid, acetic acid, formic acid etc.), CO2With H2O.Therefore, the photochemical properties of Cr (III) complex compound are based on, photolysis can effectively destroy the network of Cr (III) complex compound Structure is closed, Cr is finally discharged in the form of Cr (III) and part Cr (VI).
Invention content
1. technical problems to be solved
For Cr in the prior art (III) complexings wastewater processing technology, there are Cr (VI) high conversion rate, chromium-bearing sludge yield Greatly, the deficiencies of processing cost is high, the present invention provides a kind of reduction composite drug joint treatment with ultraviolet light trivalent chromiums, and waste water is complexed The method of recycling synchronous with chromium.The present invention irradiates the lower aqueous electron formed using the reducing property of composite drug itself with its light Strong reduction characteristic can realize to the in-situ control of Cr (VI), avoid subsequent processes, simplify technological process.
2. technical solution
The principle of the invention:Since the generation of in-situ control Cr (VI) is the difficult point for aoxidizing contact break process and being faced, and it is anti-bad The reducing agents such as hematic acid, hydroxylamine hydrochloride, sulphite, pyrosulfite, dithionite, iodized salt, borohydride salts are to Cr (VI) there is excellent reducing power.Moreover, sulphite, pyrosulfite, dithionite, iodized salt, phenol and benzene Diphenol easily generates aqueous electron (e under uv illuminationaq -), eaq -To Cr (VI) show it is excellent can also performance.Therefore, it utilizes The reducing power of reducing agent itself combines the e of its photoinduction formationaq -It is expected to realize in-situ reducing Cr (VI), reaching reduces Cr (VI) purpose generated.Solution in the pH buffer capacities of reduction composite drug and light decarboxylate control reaction process is utilized simultaneously PH remains alkalinity or alkalescent, and release Cr (III) is prone to precipitate, and is recycled.
The present invention utilizes the light sensitivity of Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound, and ligand metal charge occurs under uv radiation Transferance and be degraded;It restores composite drug under light illumination simultaneously, generates a series of intermediate free radical, such as eaq -、·H、 SO3·-、SO2·-、SO5·-、NO2·、CO2·、CO3·、S·-、N3·、·NH2、O2·-、 HO2, OH, Cr (V) and Cr (IV), these intermediate free radicals, can in-situ reducing light while the decarboxylation degradation for strengthening Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound The Cr (VI) generated in oxidation process.In addition, reduction composite drug also has certain reduction to Cr (VI), therefore, also The addition of former composite drug can be achieved to regulate and control the original position of Cr (VI).
In order to achieve the above objectives, technical solution provided by the invention is:
A method of the recycling synchronous with chromium of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water, step For:
A, it offers medicine:It is complexed in waste water to trivalent chromium and adds reduction composite drug and stir, wastewater pH is adjusted to 4~10;
B, ultraviolet light:The waste water stirred evenly is handled by ultraviolet light, chromium is precipitated with precipitated form;
C, waste liqouor:Chromium is recycled by the method for separation of solid and liquid.
Preferably, in step B, 30~180min of ultraviolet light.
Preferably, reduction composite drug include ascorbic acid, hydroxylamine hydrochloride, sodium sulfite, potassium sulfite, ammonium sulfite, Magnesium sulfite, sodium pyrosulfite, potassium metabisulfite, ammonium pyrosulfite, pyrosulfurous acid calcium, pyrosulfurous acid magnesium, connects two at calcium sulfite Sodium sulfite, potassium hyposulfite, magnesium hyposulfite, calcium hyposulfite, potassium iodide, sodium iodide, ammonium iodide, magnesium iodide, Potassium borohydride, sodium borohydride, magnesium borohydride, calcium borohydride, ammonium borohydride, phenol, catechol, resorcinol, hydroquinone, One kind in sodium nitrate, potassium nitrate, sodium nitrite, potassium nitrite, vulcanized sodium, potassium sulfide, magnesium sulfide, calcium sulfide, ammonium sulfide or It is a variety of to be combined.
Preferably, in step B, ultraviolet light processing uses launch wavelength<The light source of 400nm, including:Medium pressure mercury lamp, High-pressure sodium lamp, amalgam ultraviolet lamp, halogen lamp, xenon lamp or blackout.
Preferably, in step A, Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound is matched under ultraviolet light in stepb Body-metal electric charge transfer is acted on and is degraded;Simultaneously in the step B, reduction composite drug under light illumination, generates a series of Intermediate free radical, the intermediate free radical is while the decarboxylation degradation for strengthening Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound, and also The Cr (VI) generated in former composite drug collaboration in-situ reducing photo-oxidation process.
Preferably, restore the dosage of composite drug by reduction composite drug and chromium in water molar equivalent ratio (0.05~ 20):1 adds.
Preferably, intermediate free radical includes eaq -、·H、SO3·-、SO2·-、SO5·-、NO2·、CO2·、CO3·、 S·-、N3·、·NH2、O2·-、HO2, OH, Cr (V) and Cr (IV).
Preferably, oxide species synergistic oxidation contact break is generated in step B in ultraviolet light photolysis step;The oxide Kind includes OH, HO2·、O2·, Cr (V) and Cr (IV).
Preferably, in step B to added reduction composite drug trivalent chromium complexing waste water carry out light radiation while into Row aeration.
Preferably, chromium sediment is light green, and main component is chrome green.
A kind of application for the method restoring the recycling synchronous with chromium of composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water, The processing of waste water is complexed in Cr (III) applied to the discharge of the industries such as plating, process hides and dyestuff.
3. advantageous effect
Compared with prior art, the beneficial effects of the invention are as follows:
(1) waste water recycling synchronous with chromium is complexed in a kind of reduction composite drug of the invention joint treatment with ultraviolet light trivalent chromium Using the light sensitivity of Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound ligand-metal electric charge transfer effect occurs under uv radiation for method And it is degraded;It restores composite drug under light illumination simultaneously, generates a series of intermediate free radical, such as eaq -、·H、SO3·-、 SO2·-、SO5·-、NO2·、CO2·、CO3·、S·-、N3·、·NH2、 O2·-、HO2, OH, Cr (V) and Cr (IV), These intermediate free radicals, can in-situ reducing photooxidation while the decarboxylation degradation for strengthening Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound The Cr (VI) generated in the process;In addition, reduction composite drug also has certain reduction to Cr (VI), with intermediate free radical It can act synergistically, therefore, the addition for restoring composite drug can be achieved to regulate and control the original position of Cr (VI);
(2) waste water recycling synchronous with chromium is complexed in a kind of reduction composite drug of the invention joint treatment with ultraviolet light trivalent chromium Method, the residual concentration of total chromium is less than 1.5mg/L after processing, and the generation concentration of Cr VI is less than 0.5 mg/L, it is comprehensive to meet sewage Close the requirement of discharge standard (GB8978-2002);
(3) waste water recycling synchronous with chromium is complexed in a kind of reduction composite drug of the invention joint treatment with ultraviolet light trivalent chromium Method, reduction composite drug combined U V processing methods irradiate the lower water formed using the reducing property of composite drug itself with its light Closing the strong reduction characteristic of electronics can realize to the in-situ control of Cr (VI), avoid subsequent processes, simplify technological process;
(4) waste water recycling synchronous with chromium is complexed in a kind of reduction composite drug of the invention joint treatment with ultraviolet light trivalent chromium Method utilizes generation OH, HO in the light sensitivity and photolysis step of chromium complex2·、O2·, Cr (V) and Cr (IV) etc. it is a variety of Oxide species synergistic oxidation contact break, obtains higher remineralization efficacy;It is formed simultaneously Cr (III) and (includes the Cr of contact break release (III) and through Cr (VI) it is reduced to Cr (III)) sediment, component is more single, is chromated oxide, can direct recycling profit With.
Description of the drawings
Fig. 1 is the design sketch of present invention removal Cr-EDTA, and wherein ■ is that TOC removes curve, and zero removes curve for total chromium, △ is Cr VI formation curve.
Specific implementation mode
With reference to the accompanying drawings of the specification and specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, tests the removal of chromium in 0.2mmol/L Cr-EDTA waste water, and step is:
A, it offers medicine:Reduction composite drug is added into the waste water of 0.2mmol/L Cr-EDTA (by ascorbic acid:Hydrochloric acid hydroxyl Amine molar equivalent ratio=1:1 is combined) and stir, additive amount 2mmol/L, wastewater pH initial value 3.5,25 DEG C of temperature, it gives up PH is adjusted to 7 by water by sodium hydroxide solution;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into medium pressure mercury lamp<400nm) 180min is handled, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.23mg/L, a concentration of 0.1mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 55%.
As shown in Figure 1, removing the design sketch of Cr-EDTA for the present embodiment, wherein ■ is that TOC removes curve, and zero is total chromium Curve is removed, △ is Cr VI formation curve.
Embodiment 2
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method is applied to the removal of chromium in plating chemical industrial park waste water, and initial pH=2.3, initial chromium concn is 23.8mg/L, and TOC is dense Degree is 36mg/L, and step is:
A, it offers medicine:Be added with Cr-EDTA molar ratios be 1 ︰ 1 reduction composite drug (by sodium sulfite:Potassium sulfite mole Equivalent proportion=1:1 is combined) and it stirs, wastewater pH initial value 2.3,25 DEG C of temperature, waste water is by sodium hydroxide solution by pH It is adjusted to 8;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into high-pressure sodium lamp<400nm) 180min is handled, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.38mg/L, a concentration of 0.4mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 57%.
Embodiment 3
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment are with a concentration of 0.2mmol/L of tap water preparation Cr- citric acid wastewaters, pH=4,25 DEG C of temperature, step:
A, it offers medicine:Be added with Cr- citric acid molar ratios be 1 ︰ 2 reduction composite drug (by ammonium sulfite:Magnesium sulfite rubs That equivalent proportion=1:1 is combined) and it stirs, wastewater pH initial value 4,25 DEG C of temperature, waste water is by sodium hydroxide solution by pH It is adjusted to 6;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into amalgam ultraviolet lamp< 180min 400nm) is handled, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.2mg/L, a concentration of 0.36mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 69%.
Embodiment 4
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, it is 0.2mmol/L that experiment prepares Cr- tartaric acid waste strengths with tap water, pH=5.5,25 DEG C of temperature, and step is:
A, it offers medicine:Be added with Cr- tartaric acid molar ratios be 5 ︰ 1 reduction composite drug (by calcium sulfite:Sodium pyrosulfite Molar equivalent ratio=1:1 is combined) and it stirs, wastewater pH initial value 5.5,25 DEG C of temperature, waste water is by hydrochloric acid solution by pH It is adjusted to 5;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into halogen lamp<400nm) place 120min is managed, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.1mg/L, a concentration of 0.32mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 65%.
Embodiment 5
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepares 0.1mmol/L Cr- tartaric acid solutions with tap water and 0.1mmol/L Cr- citric acid solution equal proportions are mixed Synthesis simulated wastewater, pH=3.5,25 DEG C of temperature, step are:
A, it offers medicine:Be added with simulated wastewater molar ratio be 10 ︰ 1 reduction composite drug (by potassium metabisulfite:Pyrosulfurous acid Ammonium molar equivalent ratio=1:1 is combined) and stir, wastewater pH initial value 3.5,25 DEG C of temperature, waste water is molten by sodium hydroxide PH is adjusted to 6 by liquid;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into xenon lamp<400nm) place 180min is managed, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.35mg/L, a concentration of 0.22mg/L, TOC of Cr (VI) (total organic carbon) removal rate is about 62%.
Embodiment 6
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, using the removal of chromium in Mr. Yu's tannery waste, initial pH=3.6, initial chromium concn is 15.6 mg/L, and TOC is a concentration of 29mg/L, step are:
A, it offers medicine:Be added with Cr molar ratios be 8 ︰ 1 reduction composite drug (by pyrosulfurous acid calcium:Pyrosulfurous acid magnesium mole Equivalent proportion=1:1 is combined) and it stirs, wastewater pH initial value 3.6,25 DEG C of temperature, waste water is by sodium hydroxide solution by pH It is adjusted to 9;
B, ultraviolet light:Ultraviolet light (UV irradiations, the wavelength that the waste water of step A is passed through into blackout<400nm) place 180min is managed, chromium is precipitated with absinthe-green precipitated form, and main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.19mg/L, a concentration of 0.26mg/L, TOC of Cr (VI) (total organic carbon) removal rate is about 65%.
Embodiment 7
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, using the removal of chromium in Mr. Yu's dye house effluents, initial pH=5.5, initial chromium concn is 13mg/L, and TOC is a concentration of 32mg/L, step are:
A, it offers medicine:Be added with Cr molar ratios be 15 ︰ 1 reduction composite drug (by sodium dithionite:Potassium hyposulfite Molar equivalent ratio=1:1 is combined) and stir, wastewater pH initial value 5.5,25 DEG C of temperature does not adjust pH;
B, ultraviolet light:The waste water of step A is handled into 180min by ultraviolet light (UV irradiations), chromium is with light green Precipitated form be precipitated, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.35mg/L, a concentration of 0.35mg/L, TOC of Cr (VI) (total organic carbon) removal rate is about 61%.
Embodiment 8
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepare 0.2mmol/L Cr- oxalic acid solution equal proportions with tap water and are mixed into simulated wastewater, pH=3.5, temperature 25 DEG C, step is:
A, it offers medicine:Be added with simulated wastewater molar ratio be 1 ︰ 20 reduction composite drug (by magnesium hyposulfite:Lian Erya Calcium sulfate molar equivalent ratio=1:1 is combined) and stir, wastewater pH initial value 3.5,25 DEG C of temperature, waste water passes through hydroxide PH is adjusted to 5.5 by sodium solution;
B, ultraviolet light:The waste water of step A is handled into 180min by ultraviolet light (UV irradiations), chromium is with light green Precipitated form be precipitated, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 1.05mg/L, a concentration of 0.39mg/L, TOC of Cr (VI) (total organic carbon) removal rate is about 60%.
Embodiment 9
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepare 0.15mmol/L Cr- citric acid solution equal proportions with tap water and are mixed into simulated wastewater, pH=4, temperature 25 DEG C, step is:
A, it offers medicine:Be added with simulated wastewater molar ratio be 1 ︰ 10 reduction composite drug (by magnesium hyposulfite:Lian Erya Calcium sulfate molar equivalent ratio=1:1 is combined) and stir, wastewater pH initial value 4,25 DEG C of temperature, waste water passes through sodium hydroxide PH is adjusted to 8.5 by solution;
B, ultraviolet light:The waste water of step A is handled into 150min by ultraviolet light (UV irradiations), chromium is with light green Precipitated form be precipitated, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 0.9mg/L, a concentration of 0.27mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 65%.
Embodiment 10
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepare 0.15mmol/L Cr-NTA solution equal proportions with tap water and are mixed into simulated wastewater, pH=5, temperature 25 DEG C, step is:
A, it offers medicine:Be added with simulated wastewater Cr-NTA molar ratios be 2 ︰ 1 reduction composite drug (by magnesium hyposulfite: Calcium hyposulfite molar equivalent ratio=1:1 is combined) and stir, wastewater pH initial value 5,25 DEG C of temperature does not adjust PH;
B, ultraviolet light:The waste water of step A is handled into 180min by ultraviolet light (UV irradiations), chromium is with light green Precipitated form be precipitated, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 0.85mg/L, a concentration of 0.3mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 72%.
Embodiment 11
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepare 0.35mmol/L Cr-NTA solution equal proportions with tap water and are mixed into simulated wastewater, pH=5, temperature 25 DEG C, step is:
A, it offers medicine:Be added with simulated wastewater Cr-NTA molar ratios be 5 ︰ 1 reduction composite drug (by ascorbic acid, hydrochloric acid Azanol, sodium sulfite, potassium sulfite, ammonium sulfite, magnesium sulfite, calcium sulfite, sodium pyrosulfite, potassium metabisulfite, Jiao Ya Ammonium sulfate, pyrosulfurous acid calcium, pyrosulfurous acid magnesium, sodium dithionite, potassium hyposulfite, magnesium hyposulfite, even two sulfurous Sour calcium, potassium iodide, sodium iodide, ammonium iodide, magnesium iodide, potassium borohydride, sodium borohydride, magnesium borohydride, calcium borohydride, hydroboration Ammonium, phenol, catechol, resorcinol, hydroquinone, sodium nitrate, potassium nitrate, sodium nitrite, potassium nitrite, vulcanized sodium, sulphur Change potassium, magnesium sulfide, calcium sulfide, one or more arbitrary proportionings in ammonium sulfide to be combined, in the present embodiment by hydroquinone, Sodium nitrate and potassium nitrate molar equivalent ratio=1:1:1 is combined) and stir, wastewater pH initial value 5,25 DEG C of temperature is not adjusted PH;
B, ultraviolet light:The waste water of step A is handled into 180min by ultraviolet light (UV irradiations), chromium is with light green Precipitated form be precipitated, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 0.55mg/L, a concentration of 0.2mg/L of Cr (VI), TOC (total Organic carbon) removal rate is about 76%.
Embodiment 12
A kind of reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water recycling synchronous with chromium of the present embodiment Method, experiment prepare 0.54mmol/L Cr-NTA solution equal proportions with tap water and are mixed into simulated wastewater, pH=5, temperature 25 DEG C, step is:
A, it offers medicine:Be added with simulated wastewater Cr-NTA molar ratios be 10 ︰ 1 reduction composite drug (by ascorbic acid, hydrochloric acid Azanol, sodium sulfite, potassium sulfite, ammonium sulfite, magnesium sulfite, calcium sulfite, sodium pyrosulfite, potassium metabisulfite, Jiao Ya Ammonium sulfate, pyrosulfurous acid calcium, pyrosulfurous acid magnesium, sodium dithionite, potassium hyposulfite, magnesium hyposulfite, even two sulfurous Sour calcium, potassium iodide, sodium iodide, ammonium iodide, magnesium iodide, potassium borohydride, sodium borohydride, magnesium borohydride, calcium borohydride, hydroboration Ammonium, phenol, catechol, resorcinol, hydroquinone, sodium nitrate, potassium nitrate, sodium nitrite, potassium nitrite, vulcanized sodium, sulphur The one or more arbitrary proportionings changed in potassium, magnesium sulfide, calcium sulfide, ammonium sulfide are combined, by ammonium sulfide, iodine in the present embodiment Change magnesium and pyrosulfurous acid magnesium molar equivalent ratio=1:1:1 is combined) and stir, wastewater pH initial value 5,25 DEG C of temperature is uncomfortable Save PH;
B, ultraviolet light:By the waste water of step A by ultraviolet light (UV irradiations) handle 180min, irradiation it is same When, waste water is aerated by bottom, to accelerate the formation of precipitation, chromium to be analysed with the precipitated form of absinthe-green single-size Go out, main component is chrome green;
C, waste liqouor:By the mode of the method for separation of solid and liquid, such as miillpore filter, chromium is recycled.
After testing, in the present embodiment, remaining total chromium is 0.55mg/L, a concentration of 0.21mg/L, TOC of Cr (VI) (total organic carbon) removal rate is about 81%.
Schematically the invention and embodiments thereof are described above, description is not limiting, attached drawing Shown in be also the invention one of embodiment, actual test data is not limited thereto.So if this The those of ordinary skill in field is enlightened by it, in the case where not departing from this creation objective, is not inventively designed and is somebody's turn to do The similar frame mode of technical solution and embodiment, should all belong to the protection domain of this patent.

Claims (10)

1. a kind of method that waste water recycling synchronous with chromium is complexed in reduction composite drug joint treatment with ultraviolet light trivalent chromium, feature exist In step is:
A, it offers medicine:It is complexed in waste water to trivalent chromium and adds reduction composite drug and stir, wastewater pH is adjusted to 4~10;
B, ultraviolet light:The waste water stirred evenly is handled by ultraviolet light, chromium is precipitated with precipitated form;
C, waste liqouor:Chromium is recycled by the method for separation of solid and liquid.
It is recycled 2. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 1 is synchronous with chromium Method, it is characterised in that:In the step B, 30~180min of ultraviolet light.
It is recycled 3. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 1 is synchronous with chromium Method, it is characterised in that:The reduction composite drug includes ascorbic acid, hydroxylamine hydrochloride, sodium sulfite, potassium sulfite, Asia Ammonium sulfate, magnesium sulfite, calcium sulfite, sodium pyrosulfite, potassium metabisulfite, ammonium pyrosulfite, pyrosulfurous acid calcium, pyrosulfurous acid Magnesium, sodium dithionite, potassium hyposulfite, magnesium hyposulfite, calcium hyposulfite, potassium iodide, sodium iodide, ammonium iodide, It is magnesium iodide, potassium borohydride, sodium borohydride, magnesium borohydride, calcium borohydride, ammonium borohydride, phenol, catechol, resorcinol, right In benzenediol, sodium nitrate, potassium nitrate, sodium nitrite, potassium nitrite, vulcanized sodium, potassium sulfide, magnesium sulfide, calcium sulfide, ammonium sulfide It is one or more to be combined.
It is recycled 4. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 3 is synchronous with chromium Method, it is characterised in that:In the step B, ultraviolet light processing uses launch wavelength<The light source of 400nm, including:In Pressure mercury lamp, high-pressure sodium lamp, amalgam ultraviolet lamp, halogen lamp, xenon lamp or blackout.
It is recycled 5. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 4 is synchronous with chromium Method, it is characterised in that:In the step A, Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound is in stepb under ultraviolet light The effect of ligand metal electric charge transfer occurs and is degraded;Simultaneously in the step B, reduction composite drug under light illumination, generates A series of intermediate free radical, the intermediate free radical are same the decarboxylation degradation for strengthening Cr (III)-ammonia carboxylic/hydroxyl carboxylic complex compound When, and restore the Cr (VI) generated in composite drug collaboration in-situ reducing photo-oxidation process.
It is recycled 6. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 4 is synchronous with chromium Method, it is characterised in that:The dosage of the reduction composite drug is by the molar equivalent ratio for restoring composite drug and chromium in water (0.05~20):1 adds.
It is recycled 7. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 5 is synchronous with chromium Method, it is characterised in that:The intermediate free radical includes eaq -、·H、SO3·-、SO2·-、SO5·-、NO2·、CO2·、 CO3·、S·-、N3·、·NH2、O2·-、HO2, OH, Cr (V) and Cr (IV);Ultraviolet light photodissociation in the step B Oxide species synergistic oxidation contact break is generated in the process;The oxide species include OH, HO2·、O2·, Cr (V) and Cr (IV).
It is recycled 8. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 7 is synchronous with chromium Method, it is characterised in that:Light radiation is carried out to the trivalent chromium complexing waste water for having added reduction composite drug in the step B It is carried out at the same time aeration.
It is recycled 9. reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water according to claim 7 is synchronous with chromium Method, it is characterised in that:The chromium sediment is light green, and main component is chrome green.
10. a kind of claim 1 to 9 any the reduction composite drug joint treatment with ultraviolet light trivalent chromium complexing waste water and chromium The application of the method for synchronous recycling, it is characterised in that:Cr (III) complexings applied to the discharge of the industries such as plating, process hides and dyestuff The processing of waste water.
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